CN100347612C - Method for processing substrate and medicinal liquid used therefor - Google Patents

Abstract

A method of processing an organic film pattern formed on a substrate, includes a first step of removing an alterated or deposited layer formed at a surface of the organic film pattern, and a second step of contracting at least a part of the organic film pattern or removing a part of the organic film pattern.

Description

Substrate processing method and chemical solution used in the method

technical field

The invention relates to a substrate processing method and a chemical solution used in the method.

Background technique

The wiring circuit is usually formed by, for example, forming an organic film pattern on a semiconductor wafer, an LCD (liquid crystal display) substrate, or other substrates, and by using the organic film pattern as a mask to perform etching of the bottom mold or the substrate, The patterning process of the base film is thereby performed, and the organic film pattern is removed after the patterning process of the base film.

For example, JP No. 8-23103 proposes a method of forming a wiring circuit, which includes the steps of forming an organic film pattern (referred to as "resist pattern" in the publication) on a substrate, by performing the following steps: The organic film pattern is the etching of the mask, and one or two layers of bottom film are patterned, and the organic film pattern is developed, that is, the organic film pattern is overdeveloped, and the overdeveloped organic film pattern is used as a mask , Carry out another pattern forming treatment on one or two layers of bottom film. Form the base film into a cone shape or a step shape. Thus, a wiring circuit with high resistance to dielectric breakdown is formed. After the re-patterning process of the base film, the organic film pattern is removed by a lift-off process.

Figure 1 is a flowchart for carrying out the method described in the above publication.

As shown in Figure 1, the steps included in the method are in order: coating an organic film (ie, photoresist) on the conductive film formed on the substrate, exposing the organic film (step S01), developing treatment (step S02 ), and prebaking or heating treatment (step S03 ), thus forming an initial organic film pattern on the substrate. The method further includes the following steps in order: using the organic film pattern as a mask to etch the conductive film on the substrate (step S04), overdeveloping the organic film pattern (step S101), and Perform prebaking or heat treatment (step S102 ), and pattern the organic film to form a new pattern.

The method further includes the following steps: using the overdeveloped organic film pattern as a mask, half-etching the conductive film to make the cross-sectional shape of the conductive film step-like, so as to prevent the cross-section from becoming vertical or inverted.

However, this method has a problem in that in the etching process of the conductive film (step S04 ), the original organic film pattern is actually damaged, resulting in the formation of a degenerated layer and/or a deposited layer on the organic film pattern.

The thus formed altered layer and/or deposited layer (hereinafter referred to as "damaged layer") hinders the second development of the organic film pattern (step S101). That is, since the damaged layer covers the surface of the organic film pattern, it is difficult to smoothly develop the organic film pattern.

The progress of excessive development differs depending on the state of the damaged layer. If the etching process (step S04 ) is wet etching, the chemical solution and temperature used will greatly affect the condition of the damaged layer. On the other hand, if the etching process (step S04 ) is dry etching, the type of gas used, the pressure of the process, and the discharge method will have a great impact on the condition of the damaged layer. Moreover, different types of gases used will result in different chemical damage to the organic film pattern, and different treatment pressures and discharge methods will result in different physical impacts of the ionized gas or free radical gas on the organic film pattern. Wet etching causes less damage to the organic film pattern than dry etching, so the damage layer produced by wet etching hinders the development of the organic film pattern to a lesser degree than the damage layer produced by dry etching.

As mentioned above, due to the existence of the damaged layer, the over-development treatment of the organic film pattern cannot be carried out smoothly, resulting in non-uniform over-development treatment of the organic film pattern. uniformity problem.

JP No. 2002-534789 based on WO 00/41048 (PCT/US99/28593) proposes an apparatus for use in a synchronous system for processing substrates. Specifically, the device includes a wafer cluster tool with a scheduler that synchronizes all events in the system with each other.

JP No. 10-247674 proposes an apparatus for processing a substrate, which includes: a plurality of processors, each of which performs a series of processes on a substrate; and a carrier that transports the substrate into each processor. The transport tool comprises: a transport plate; a first rotator rotatable around a first rotation axis extending perpendicularly to the transport plate; a first transmission for rotating the first rotator; A second rotator rotating on a second rotational axis extending perpendicularly to the first rotator; a second actuator for rotating the second rotator; a substrate support rotatable about a third rotational axis a rotator, the third axis of rotation extending perpendicular to the second rotator, the substrate holder supporting the substrate; and a third actuator for driving the substrate holder.

Brief description of the invention

In view of the above-mentioned problems in the prior art, an object of the present invention is to provide a method of processing a substrate which enables smooth overdevelopment of an organic film pattern formed on the substrate.

The present invention also provides the medicinal solution used in the above method.

One aspect of the present invention provides a method for processing an organic film pattern formed on a substrate, which includes the steps of: first step, removing the degenerated layer or deposition layer formed on the surface of the organic film pattern; second step, shrinking the organic film At least a portion of the pattern, or removing a portion of the pattern of the organic film.

The organic film pattern initially formed on the substrate may have a uniform thickness, but preferably the organic film pattern initially formed on the substrate has at least two portions having different thicknesses from each other.

In order for the organic film pattern to have at least two portions having different thicknesses from each other, the organic film pattern may be exposed to at least two different lights. Specifically, two or more grating masks having transmittances different from each other may be used. The organic film pattern is developed by exposing the organic film pattern to two or more different levels of light, so that the more or less exposed parts of the organic film pattern are thinned, resulting in the formation of two or more layers having different thicknesses from each other. part of the organic film pattern.

The history of the initial exposure of the organic film pattern remains in the organic film pattern, and therefore, the portion having a small thickness can be further thinned or removed by performing a development process as a second development process on the organic film pattern.

For the chemical solution with the function of developing the organic film pattern used in the second step, if a positive developer is used in the development process for forming the original organic film pattern, then also use the developer with the function of positive development. The development process for forming the initial organic film pattern uses a negative developer, and a developer having a negative development function is also used.

The step of thinning or removing the thinner film portion can be performed by keeping the organic film in a non-photosensitive state before performing the first step.

In addition, the step of determining a new pattern of the organic film pattern can be appropriately performed by keeping the organic film in a non-photosensitive state before performing the first step.

The present invention additionally provides a processing method for an organic film pattern formed on a substrate, which includes a first step of removing the degenerated layer formed on the surface of the organic film pattern to reveal the unaltered part of the organic film pattern; a second step of reducing the size of the organic film pattern. at least a part of the organic film pattern, or remove a part of the organic film pattern.

The present invention additionally provides a processing method for an organic film pattern formed on a substrate, which includes a first step of removing a degenerated layer formed on the surface of the organic film pattern to make the organic film pattern appear; a second step of shrinking the organic film pattern at least a part of the organic film pattern, or remove a part of the organic film pattern.

Another aspect of the present invention provides the chemical solution used in the above method, which contains 0.01% by weight to 10% by weight (inclusive) of amine-based materials.

The method of the present invention may additionally include the step of heating the organic film pattern. The purpose of the heat treatment is to remove moisture, acid solution and/or alkali solution infiltrated in the organic film pattern, or restore the adhesive force between the organic film pattern and the base film when the adhesive force is decreased. This heat treatment of the organic film pattern is performed at a temperature of, for example, 50-150° C. for 60-300 seconds.

The organic film pattern can be completely removed by the method of the present invention. This means that the method of the present invention can be used for peeling or separation treatment of organic film patterns.

The aforementioned advantages of the present invention are described in detail below.

Since the method of the present invention includes the first step of removing the altered or deposited layer formed on the surface of the organic film pattern, the second step of reducing at least a portion of the organic film pattern or removing a portion of the organic film pattern can be smoothly performed.

If the second step is to develop the organic film pattern two or more times, it is beneficial to promote the penetration of the chemical liquid having the function of developing the organic film pattern into the organic film pattern and uniformly develop the organic film pattern. The same effect can be obtained even if the second step is performed using a chemical solution that does not have the function of developing the organic film pattern but has the function of dissolving the organic film pattern.

Description of drawings

FIG. 1 is a flowchart showing the steps of a conventional method for performing substrate processing.

Fig. 2 is a plan view of an example of an apparatus for processing a substrate.

Fig. 3 is a plan view of another example of an apparatus for processing a substrate.

FIG. 4 is a schematic diagram showing a candidate processing unit for installation in an apparatus for processing a substrate.

Fig. 5 is a cross-sectional view of an example of a unit for performing chemical treatment on an organic film pattern.

Fig. 6 is a flowchart of the steps performed in a method of processing a substrate according to the first embodiment of the present invention.

Fig. 7 is a flowchart of steps performed in an example of a method of processing a substrate according to the first embodiment of the present invention.

Fig. 8 is a flowchart of steps performed in a method of processing a substrate according to a second embodiment of the present invention.

Fig. 9 is a flowchart of steps performed in a method of processing a substrate according to a third embodiment of the present invention.

Fig. 10 is a flowchart of steps performed in a method of processing a substrate according to a fourth embodiment of the present invention.

Fig. 11 is a flowchart of steps performed in a method of processing a substrate according to a fourth embodiment of the present invention.

Fig. 12 is a flowchart of the steps performed in the first example of the method for processing a substrate according to the fourth embodiment of the present invention.

Fig. 13 is a flow chart of the steps performed in the second example of the method for processing a substrate according to the fourth embodiment of the present invention.

FIG. 14 shows the degree of degeneration of the degenerated layer according to the cause of the degenerated layer.

Fig. 15 is a schematic diagram showing the relationship between the concentration of amine materials in the liquid medicine and the removal rate.

FIG. 16 shows changes in the degenerated layer when only ashing treatment is performed on the degenerated layer.

Fig. 17 shows changes in the degenerated layer when only chemical solution treatment is performed on the degenerated layer.

FIG. 18 shows changes in the degenerated layer when ashing treatment and chemical solution treatment are sequentially performed on the degenerated layer.

preferred embodiment

The substrate processing method according to the embodiment of the present invention is performed by using, for example, the substrate processing apparatus 100 shown in FIG. 2 or the substrate processing apparatus 200 shown in FIG. 3 .

Apparatus 100 and 200 are designed so as to selectively include a processing unit for performing various processing on a substrate, which will be described later.

For example, as shown in FIG. 4, the apparatus 100, 200 may have six processing units: a first processing unit 17 for exposing the organic film pattern, a second processing unit 18 for heating the organic film pattern, and a second processing unit 18 for controlling the organic film pattern. The third processing unit 19 for the pattern temperature, the fourth processing unit 20 for developing the organic film pattern, the fifth processing unit 21 for implementing chemical liquid treatment on the organic film pattern, and the ashing process for implementing the organic film pattern The sixth processing unit 22 .

In the first processing unit 17 for organic film pattern exposure, exposure processing is performed on the organic film pattern formed on the substrate. The organic film pattern covering at least a portion of the substrate may be exposed. For example, the organic film pattern may be exposed completely covering the substrate or covering at least 1/10 of the total area of the substrate. In the first processing unit 17 for exposure of the organic film pattern, the organic film pattern can be fully exposed at one time, or can be scanned and exposed with a spotlight in a predetermined area of the organic film pattern. For example, light used for pattern exposure of the organic film is ultraviolet rays, fluorescent light, or natural light.

In the second processing unit 18 for heating the organic film pattern, the substrate or the organic film pattern is subjected to heat treatment or drying treatment, and the treatment temperature can be in the range of, for example, 80°C-180°C, or 100°C-150°C . The second processing unit 18 includes a stage that supports the substrate in a horizontal state, and a box in which the stage is disposed.

The third processing unit 19 controls the temperature of the organic film pattern or the substrate. For example, the third processing unit 19 keeps the temperature of the organic film pattern and/or the substrate in the range of, for example, 10°C-50°C, or 10°C-80°C. The third processing unit 19 includes a stage that supports the substrate in a horizontal state, and a box in which the stage is disposed.

In the fifth processing unit 21, the organic film pattern or the substrate is treated with a chemical solution.

As shown in FIG. 5 , the fifth processing unit 21 includes, for example, a chemical solution tank 301 storing a chemical solution, and a tank 302 in which a substrate 500 is disposed. The box body 302 includes: a movable nozzle 303 for supplying the liquid medicine pumped by the liquid medicine tank 301 onto the substrate 500, a platform 304 for supporting the substrate 500 in an almost horizontal state, and discharging waste liquid and gas from the box body 302. The discharge port 305.

In the fifth processing unit 21 , by pumping nitrogen gas into the chemical solution tank 301 , the chemical solution in the chemical solution tank 301 can be supplied onto the substrate 500 through the movable nozzle 303 . Also, the movable nozzle 303 can move in the horizontal direction. Platform 304 includes a plurality of upstanding pegs to support substrate 500 from the lower surface.

The fifth processing unit 21 may also be of a dry type that vaporizes the chemical solution and applies the vaporized chemical solution on the substrate 500 .

For example, the chemical solution used in the fifth processing unit 21 includes at least one of acid solution, organic solvent and alkali solution.

In the fourth processing unit 20 for organic film pattern development, the organic film pattern or the substrate is developed. For example, the fourth processing unit 20 may be designed to have the same structure as the fifth processing unit 21 except that the developer is stored in the chemical solution tank 301 .

In the sixth processing unit 22, the organic film pattern formed on the substrate 500 is etched by the following processing or other processing: plasma processing (oxygen plasma or oxygen/fluorine plasma), use Photoenergy treatment of light, and ozone treatment using light energy or heat.

As shown in FIG. 2, the substrate processing apparatus 100 includes: a first box stage 1, wherein a box L1 for storing a substrate (such as an LCD substrate or a semiconductor wafer) is placed; a second box stage 2, wherein a and Cassette L2 identical to cassette L1; processing unit arrangement areas 3 to 11 each of which is respectively provided with processing units U1 to U9; substrate transfer between first and second cassette stages 1 and 2 and respective processing units U1 to U9 A substrate transfer robot 12; a controller 24 for controlling the robot 12 to transfer substrates and controlling the processing units U1 to U9 to perform various processes.

For example, the box L1 is used to store substrates before being processed by the substrate processing apparatus 100 , and the box L2 is used to store substrates processed by the substrate processing apparatus 100 .

Any one of the six processing units shown in FIG. 4 can be selected as each of the processing units U1 to U9 arranged in the processing unit configuration area 3-11.

The number of processing units can be adjusted according to the type or processing capacity of the processing units. Therefore, no processing unit may be arranged in any one or more of the processing unit configuration areas 3 to 11 .

The controller 24 selects a program according to the processing to be performed in each of the processing units U1 to U9 and the automaton 12 and executes the selected program, thereby controlling the operations of the processing units U1 to U9 and the automaton 12 .

Specifically, the controller 24 controls the order in which the robot 12 transfers the substrates according to the data related to the processing order, thereby taking out the substrates from the first and second cassette stages 1, 2 and the respective processing units U1 to U9, and Substrates are added in the specified order.

In addition, the controller 24 operates the processing units U1 to U9 according to data related to processing conditions.

The apparatus 100 shown in FIG. 2 is designed to be able to change the order of processing to be performed by the processing units.

In contrast, in the apparatus 200 shown in FIG. 3 , the order of processing to be executed by the processing means is fixed.

As shown in FIG. 3 , the device 200 includes: a first box table 13 on which a box L1 is placed; a second box table 16 on which a box L2 is placed; processing unit configuration areas 3 to 9 respectively equipped with processing units U1 to U7; A first robot 14 that transfers substrates between cassette L1 and processing unit U1; a second robot 15 that transfers substrates between processing unit U7 and cassette L2; and controls the first and second robots 14 and 15 A controller 24 that transfers substrates to processing units U1 through U7 for various processing operations.

In the apparatus 200, the order of processing performed by the processing units is fixed. Specifically, continuous processing starts from a processing unit located upstream, and is performed in the direction of arrow A in FIG. 3 .

Each of the processing units U1 to U7 to be arranged in the processing unit configuration areas 3 to 9 is selected from any one of the six types of processing units shown in FIG. 4 . The number of processing units can be appropriately determined according to the type of processing or processing capacity. Therefore, no processing unit may be arranged in any one or more of the processing unit configuration areas 3 to 9 .

Apparatus 100 and 200 are designed to include: a unit for transporting a substrate (specifically a robot), a unit for storing a cassette therein (specifically a cassette station) and a processing unit selected from the six processing units shown in FIG. unit to process organic film patterns formed on substrates.

Although the devices 100 and 200 shown in FIG. 2 and FIG. 3 are designed to include nine and six processing units respectively, these numbers can also be appropriately increased or decreased according to the type of processing, the capacity of the processing units, and the cost.

In addition, although the devices 100 and 200 are designed to include two boxes L1 and L2, the number thereof can be appropriately increased or decreased according to the required capacity, cost and the like.

Devices 100 and 200 may include processing units other than the six processing units shown in FIG. 4 . For example, apparatuses 100 and 200 may include a processing unit for exposing a substrate to form a small pattern, a processing unit for wet or dry etching a substrate, a processing unit for coating a resist film on a substrate, a processing unit for A processing unit for strengthening the adhesive force between the substrate and the organic film pattern, or a processing unit for washing the substrate (by dry cleaning using UV light or plasma, and wet cleaning using cleaning liquid).

When the apparatuses 100 and 200 include a processing unit for wet or dry etching of a substrate, it is possible to pattern an underlying film (eg, a substrate surface) using an organic film pattern as a mask.

If the fifth processing unit 21 includes a chemical solution capable of etching the bottom film, specifically an etchant containing acid or alkali, the fifth processing unit 21 can be used as a processing unit for wet or dry etching of the substrate.

In order to make the processes uniform, the apparatuses 100 and 200 may comprise a plurality of common processing units for performing multiple common processes on the substrate.

When the apparatuses 100 and 200 comprise a plurality of common processing units for performing multiple common processes on the substrate, preferably the substrates are processed in the common processing units so that the substrates are oriented in different directions from each other in the common processing units (e.g. reverse). In this case, it is preferred that the apparatuses 100 and 200 are designed to have different orientations of the substrates in the processing unit to ensure that the orientation of the substrates can be done automatically rather than manually.

When apparatuses 100 and 200 comprise a single processing unit, preferably the substrates are processed in the processing unit multiple times, with the substrates facing different directions from each other in each processing. For example, substrates are preferably processed in multiple directions opposite to each other, in which case it is preferred that apparatuses 100 and 200 are designed to function in one processing unit to process substrates with the substrates facing each other in each processing different directions.

It is also preferred that the substrate is processed in a first orientation in one processing unit and then processed in a second orientation different from the first orientation, in which case it is preferred that apparatuses 100 and 200 are designed to function in such a way.

Preferred embodiments of the present invention are described below.

The methods of the following embodiments are implemented on an organic film pattern composed of a photosensitive organic film formed on a substrate. In this method, a damaged layer (altered layer or deposited layer) formed on the surface of an organic film pattern is removed by a first step, and then, at least a part of the organic film pattern is reduced, or a part of the organic film pattern is removed, in a second process. .

(first embodiment)

Fig. 6 is a flowchart of steps performed in a method of processing a substrate according to the first embodiment of the present invention.

In the method of the first embodiment, after removing the altered layer or deposited layer formed on the surface of the organic film pattern, at least the organic film pattern is reduced by performing a development treatment (for example, a second development treatment) on the organic film pattern. part, or remove part of the organic film pattern.

The organic film is patterned on the substrate in a conventional manner, for example by photolithography.

Specifically, an organic film is coated on the substrate, and then, as shown in FIG. organic film (step S03 ), forming an initial organic film pattern on the substrate.

The pre-baking or heating of the organic film (step S03 ) performed after the organic film development treatment (step S02 ) serves as the pre-baking or heating of the organic film (resist film) performed before the organic film development over-treatment. Considering that the photosensitive group in the organic film is decomposed and the resin is cross-linked at high temperature, the pre-drying or heating of the organic film (step S03) is not carried out at such a high temperature, so as to prevent the organic film from being unable to be processed during the excessive development process. Process again. Specifically, the pre-drying or heating of the organic film (step S03 ) is performed at a temperature of at most 140°C. For example, the pre-baking or heating of the organic film (step S03 ) is performed at a temperature equal to or lower than that of the pre-baking of the organic film (50 to 130° C.). For the reasons described above, it is possible to control the rate of excessive development by controlling the temperature at which prebaking or heating (step S03 ) of the organic film is carried out.

An initial organic film pattern may be formed on the substrate by, for example, a printing method, and in this case, the development treatment of the organic film performed after removing the altered layer and the deposited layer is the first development treatment.

Therefore, as shown in FIG. 6, the base film under the organic film pattern, that is, the surface of the substrate is etched using the original organic film pattern as a mask (step S04).

The method of the first embodiment has another process after the etching process (step S04).

Specifically, as shown in FIG. 6, in the method of the first embodiment, after the chemical solution treatment (step S11) is performed on the organic film as a pretreatment (first treatment), the organic film pattern development treatment ( Step S12) and heating the organic film pattern (step S13) as main processing (second processing).

In performing chemical solution treatment on the organic film pattern (step S11 ), the chemical solution (acid solution, alkaline solution or organic solvent) is applied on the organic film pattern to remove the deteriorated layer or deposition layer formed on the surface of the organic film pattern. The chemical solution treatment (step S11 ) on the surface of the organic film is carried out in the fifth treatment unit 21 .

In the chemical liquid treatment (step S11 ) of the organic film pattern, the implementation time of this step and the chemical liquid to be used can be determined so as to remove only the damaged layer (deteriorated layer or deposited layer).

In implementing the chemical solution treatment to the organic film pattern (step S11), if a degenerated layer is formed on the surface of the organic film pattern without forming a deposition layer, the degenerated layer is selectively removed, and if a degenerated layer and a deposition layer are formed on the surface of the organic film pattern , the altered layer and the deposition layer are removed, and if the deposition layer is formed instead of the altered layer on the surface of the organic film pattern, the deposition layer is selectively removed.

As a result of removing the altered layer and/or the deposited layer, the unaltered portion of the organic film pattern, or the organic film pattern covered by the deposited layer, is revealed.

For example, the deposited layer removed by the pretreatment (step S11) is formed by the deterioration of the surface of the organic film pattern, and the factors causing the deterioration are as follows: aging, thermal oxidation, thermal hardening, adhesion of the deposited layer to the organic film pattern, use Wet etching of an organic film pattern by an acid etchant, ashing treatment (eg, O ₂ ashing treatment) of an organic film pattern, or dry etching using a dry etching gas. That is, the organic film pattern is degraded due to physical and chemical damage due to the above factors. Since the degree of deterioration and the characteristics of the metamorphic layer vary greatly according to the following factors, the difficulty of removing the metamorphic layer also varies accordingly: the chemical solution used in the wet etching process; the dry etching process (plasma application) is isotropy or anisotropy; the presence or absence of deposits on the organic film pattern; the gas used in the dry etching process.

The deposited layer to be removed by the pre-processing (step S11) is due to the normal etching process. The characteristics of the deposited layer also vary greatly with the following factors, so the difficulty of removing the deposited layer also varies accordingly: whether the dry etching process is isotropic or anisotropic; the use of gas.

Therefore, the time for performing the pretreatment (step S11 ) and the chemical solution used in the pretreatment (step S11 ) need to be appropriately set or selected according to the ease of removal of the degenerated layer or the deposited layer.

For example, as the chemical solution used in the pretreatment (step S11), a chemical solution containing basic chemicals, a chemical solution containing acidic chemicals, a chemical solution containing organic solvents, a chemical solution containing organic solvents and amine-based materials can be selected. materials, or solutions containing alkaline chemicals and amine materials.

For example, the above-mentioned basic chemical may contain an amine-based material and water, and the above-mentioned organic solvent may contain an amine-based material.

The chemical solution used in the pretreatment (step S11) may also contain a preservative.

For example, the amine material is selected from: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine , tributylamine, hydroxylamine, diethylhydroxylamine, dehydrated diethylhydroxylamine, pyridine and picoline. The medical solution may contain one or more amine materials selected therefrom.

The content of the amine material in the liquid medicine is preferably 0.01% by weight to 10% by weight (inclusive), more preferably 0.05% by weight to 3% by weight (inclusive), most preferably 0.05% by weight to 1.5% by weight ( including end values).

The pre-treatment (step S11) has the following advantages: the chemical solution having the function of developing the organic film pattern can easily penetrate into the organic film pattern in the subsequent step (that is, over-development (step S12)), thereby improving the over-development Processing quality and efficiency.

The second developing process or over-developing process (step S12 ) of the organic film pattern is performed in the fourth processing unit 20 for shrinking at least a part of the organic film pattern on the substrate or removing a part of the organic film pattern.

In the fourth processing unit 20 , the organic film pattern formed on the substrate is developed using a chemical solution having the function of developing the organic film pattern.

As for the chemical solution having the function of developing the organic film pattern, it can be selected from: an alkaline aqueous solution containing 0.1 to 10.0% by weight of TMAH (tetramethylammonium hydroxide), or an inorganic alkaline aqueous solution such as NaOH or CaOH.

In heating the organic film pattern (step S13), the substrate is placed on a platform kept at a predetermined temperature (for example, 80 to 180° C.) in the second processing unit 18, and kept for a predetermined time (for example, 3 to 5 minutes) ). By performing this step, the chemical liquid having the function of developing the organic film pattern implemented on the substrate in the over-development treatment (step S12) can be infiltrated into the organic film pattern, which is beneficial to the organic film pattern through the over-development treatment. Shrink or remove.

Preferably, after step S13 is performed, the temperature of the substrate is cooled to about room temperature.

As described above, the main processing for reducing at least a part of the organic film pattern or removing a part of the organic film pattern includes over-development processing (step S12 ) and heat processing (step S13 ).

Shrinking at least a part of the organic film pattern includes: reducing the volume of the organic film pattern without changing its area (ie, thinning at least a part of the organic film pattern), and reducing the area of the organic film pattern. Removal of a part of the organic film pattern is accompanied by a reduction in the area of the organic film pattern.

Performing the main processing in this embodiment has any of the following purposes.

(A) By reducing the area of the organic film pattern, the organic film pattern is changed into a new pattern.

(B) removing at least a part of the organic film pattern for separating a part of the organic film pattern into a plurality of parts, thereby changing the organic film pattern into a new pattern.

(C) Before and after the processes of (A) and (B), respectively, use the organic film pattern as a mask to perform etching treatment on the base film, so that the etching process (step S04) before the excessive development process (step S12) ) is different from that in the etching process after steps S12 and S13.

(D) By performing the treatment (C), the base film (for example, the surface of the substrate) under the organic film pattern is processed into a cone shape (the upper part becomes thinner) or a step shape.

The process of processing the bottom film into a stepped shape may include half-etching the bottom film (eg, conductive film) using the over-developed organic film pattern as a mask. Such treatment can change the cross-sectional shape of the bottom membrane into a step shape, thereby preventing the cross-section from becoming vertical or becoming an inverted cone.

(E) When the bottom film under the organic film pattern is a multi-layer structure, any at least two layers in the bottom film can be etched into different patterns through the above step (C).

(F) As an example of the processes (A) and (B), assuming that the organic film pattern is made of an insulating material, after the substrate is etched (step S04) before the over-development process (step S12), the organic film pattern is made of an insulating material. The film pattern is deformed so that the organic film pattern functions as an insulating film covering only the circuit pattern.

(G) when the original organic film pattern has at least two parts having different thicknesses from each other, performing (A) or (B) treatment by selectively removing only a small thickness of the parts, and subsequent (C) Go to (F) for processing.

(H) shrinking or thinning at least a part of the organic film pattern. Through such an operation, at least a part of the organic film pattern can be easily removed.

At least a part of the organic film pattern may be removed by performing the treatment (H) until the base film appears.

(I) When the original organic film pattern has at least two portions different in thickness from each other, only a portion having a small thickness is thinned among the portions, ensuring that the portion can be easily removed.

Step (I) is substantially the same as step (G) if the step (I) is carried out until the base film appears.

An example of step (G) will be described below with reference to FIG. 7 .

7 is a flow chart of steps for selectively removing only a portion having a small thickness among the portions when an initial organic film pattern has at least two portions having different thicknesses from each other.

Figure 7(a-2), Figure 7(b-2), Figure 7(c-2) and Figure 7(d-2) are plan views respectively, and Figure 7(a-1) is the Sectional view, Fig. 7 (b-1) is the sectional view of Fig. 7 (b-2), Fig. 7 (c-1) is the sectional view of Fig. 7 (c-2), Fig. 7 (d-1) is the sectional view of Fig. 7(d-2) Section view.

As shown in FIG. 7(a-1) and FIG. 7(a-2), a gate electrode 602 having a predetermined shape is formed on an insulating substrate 601 . A gate insulating film 603 is formed on the insulating substrate 601 to cover the gate electrode 602, and an amorphous silicon layer 604, an N ⁺ amorphous silicon layer 605, and a source/drain layer are sequentially deposited on the gate insulating film 603 606.

As shown in FIG. 7(b-1) and FIG. 7(b-2), an initial organic film pattern 607 is formed on the source/drain layer 606 (steps S01 to S03), and then the organic film pattern 607 is used as The mask etches the source/drain layer 606, the N ⁺ amorphous silicon layer 605 and the amorphous silicon layer 604 (step S04). As a result, the gate insulating film 603 appears in a region not covered by the organic film pattern 607 .

The organic film pattern 607 is formed so as to partially cover the thin portion 607 a of the gate insulating film 603 . An organic film pattern having two kinds of thicknesses can be formed by making the exposure amounts of the portion which is the thin portion 607a and the portion other than 607a different from each other.

Then, preprocessing (step S11 of chemical solution treatment on the organic film pattern) and main processing (step S12 of developing the organic film pattern and step S13 of heating the organic film pattern) are performed. The history of exposure at the time of forming the first organic film pattern 607 also remains in the organic film pattern 607 . Therefore, by performing the main process (step S12 and step S13), only the thin portion 607a of the organic film pattern 607 is selectively removed, as shown in FIG. 7(c-1) and FIG. 7(c-2). That is, the original organic film pattern 607 is divided into a plurality of parts (two parts in FIG. 7).

Then, using the organic film pattern 607 as a mask, the source/drain layer 606 and the N ⁺ amorphous silicon layer 605 are etched, so that the amorphous silicon layer 604 appears, and then the organic film pattern 607 is removed.

When the original organic film pattern is formed in a plurality of portions having different thicknesses, the organic film can be patterned into a new pattern by removing only a thin portion of the plurality of portions of the organic film pattern. Specifically, by separating the film-coated pattern into multiple parts (for example, two parts as shown in FIG. 7(c-2)), the organic film can be patterned to form a new pattern.

When the base film under the organic film pattern is composed of multiple layers, before and after the above-mentioned processing step S11, step S12 and step S13, the base film is etched with the organic film pattern as a mask, so that the over-developed The region etched in the etching process (step S04 ) performed before the process (step S12 ) and the region etched in the etching process performed after steps S12 and S13 are different from each other. Therefore, the first layer (such as the amorphous silicon layer 604) and the second layer (such as the source/drain layer 606 and the N ⁺ amorphous silicon layer 605) of the multiple layers of the bottom film can be etched to form different patterns from each other.

A specific example of the substrate processing apparatus used for performing the method of the first embodiment will be described below.

The substrate processing apparatus used in performing the method of the first embodiment includes an apparatus 100 or 200 including a fifth processing unit 21 as processing units U1 to U9 or U1 to U7, a fourth processing unit 20, and a second processing unit 20. Substrate processing for unit 18.

In the device 100, the arrangement of the fifth processing unit 21, the fourth processing unit 20 and the second processing unit 18 is arbitrary.

In contrast, in the substrate processing apparatus 200 , the fifth processing unit 21 , the fourth processing unit 20 and the second processing unit 18 are sequentially arranged in the direction of arrow A in FIG. 3 . Similarly, in the method described below, each processing unit in the device 200 needs to be arranged in a predetermined order.

The step S13 of heating the organic film pattern can be omitted, and in this case, the apparatus 100 or 200 does not need to include the second processing unit 18 . In the following FIGS. 8 to 11 , like step S13 , steps enclosed in brackets mean that they can also be omitted. In addition, the processing units corresponding to the steps enclosed in brackets can also be omitted.

Even if the same step is performed multiple times (eg even if step S4 is performed twice), the apparatus 100 includes a single processing unit for performing this step. In contrast, device 200 necessarily includes the same processing unit as many times as performing the same step. For example, if step S4 is to be performed twice, the device 200 needs to include two second processing units 18 . This point is the same in each of the substrate processing methods described below.

In the method of the first embodiment, since the pretreatment is performed first to remove the altered layer or deposition layer formed on the surface of the organic film pattern, and then the main treatment is performed to shrink or remove at least a part of the organic film pattern. Therefore, the main processing can be performed smoothly. That is, it is possible to contribute to the permeation of the chemical solution having the function of developing the organic film pattern into the organic film pattern, and to uniformly develop the organic film pattern.

(second embodiment)

Figure 8 is a flow chart showing the steps carried out in the method for carrying out the second embodiment of the present invention.

As shown in FIG. 8, compared with the method of the first embodiment, the method of the second embodiment additionally includes a step of ashing the organic film pattern (step S21) before main processing (steps S12 and S13).

That is, the method of the second embodiment differs from the method of the first embodiment only in that it additionally includes an ashing process (step S21) of the organic film pattern, which is different from that of the first embodiment in addition to the ashing process (step S21). The scheme approach is the same.

In the method of the second present embodiment, an ashing treatment is performed on the organic film pattern (step S21 ), thereby removing the altered layer or deposited layer formed on the surface of the organic film pattern.

The ashing process (step S21) is carried out in the sixth processing unit 22

For the ashing treatment (step S21), dry processing can be carried out: as implementing plasma on the organic film pattern in an oxygen or oxygen/fluorine atmosphere; implementing light energy with a short wavelength such as ultraviolet rays on the organic film pattern; The pattern implements ozone. That is, light energy or heat is applied to the organic film pattern.

The execution time of the ashing treatment (step S21) is preferably set so that only the altered layer or the deposited layer is removed.

As a result of removing the altered or deposited layer, as in the first embodiment described above, the unaltered portion of the organic film pattern is revealed, or the organic film pattern covered by the deposited layer is revealed.

The ashing treatment (step S21) as a pretreatment can provide the advantage that the chemical solution having the function of developing the organic film pattern can easily penetrate into the organic film in the subsequent step (i.e., over-development treatment (step S12)). In the pattern, that is, it plays a role in improving the quality and effect of excessive development.

Subsequent processing is the same as that in the first embodiment, so description thereof is omitted.

The second embodiment offers the same advantages as the first embodiment described.

In addition, since the ashing treatment (step S21) is performed on the organic film pattern as a pretreatment, even if the degenerated layer and the deposited layer are relatively stubborn and difficult to remove only by excessive development treatment (step S21), these degenerated layers can also be removed. , deposits are easily removed.

(third embodiment)

Figure 9 is a flow chart of the steps implemented in the method for carrying out the third embodiment of the present invention.

As shown in FIG. 9, the method of the third embodiment includes performing ashing treatment on the organic film pattern (step S21) and implementing chemical solution treatment on the organic film pattern (step S11), both of which are pre-treatments and include over-developing. Both the treatment (step S12) and the heat treatment (step S13) serve as the main treatment.

That is, in the method of the third embodiment, only in that the pretreatment includes a combination of ashing treatment (step S21) on the organic film pattern and chemical solution treatment (step S11) on the organic film pattern is performed compared with the first method. The method of the embodiment is different, and other aspects are the same as the method of the first embodiment.

In the first embodiment, the pretreatment includes wet treatment (step S11). In contrast, the pre-processing of the third embodiment includes dry processing (step S21) and wet processing (step S11). Therefore, the surface of the altered or deposited layer is removed by dry treatment, ie, ashing treatment (step S21 ), while the rest of the altered or deposited layer is removed by wet treatment, ie, chemical solution treatment (step S11 ).

The method of the third embodiment provides the same advantages as those obtained with the first embodiment.

Also, even if it is difficult to remove the altered or deposited layer only by performing chemical treatment (step S12), the layer can be removed by performing ashing treatment (step S21) before performing chemical treatment (step S12).

The ashing treatment (step S21 ) performed in the pretreatment is to remove the surface of the altered layer or the deposited layer. Therefore, compared with the second embodiment, the ashing treatment time can be shortened to ensure that the damage to the base film caused by the ashing treatment can be reduced.

Compared with the chemical liquid used in the step S11 of the first embodiment, the chemical liquid used in the step S11 of the third embodiment can use a chemical liquid that is less erosive to the organic film pattern, or make the chemical liquid of the third embodiment The processing time of step S11 is shorter than that of step S11 of the first embodiment.

(fourth embodiment)

10 and 11 are flowcharts of the steps performed in the method of the fourth embodiment of the present invention.

In FIGS. 10 and 11, the steps S01 to S03 of forming the initial organic film pattern on the substrate, and the etching step S04 of the base film are not omitted.

As shown in FIGS. 10 and 11 , the method of the fourth embodiment further includes performing an exposure treatment of the organic film pattern (step S41 ) before performing the methods of the first to third embodiments.

As shown in Figure 10(a), Figure 10(b) and Figure 10(c), the exposure treatment (step 41) of the organic film pattern can be carried out before the pretreatment, or alternatively, as shown in Figure 10(d) As shown, the exposure treatment of the organic film pattern (step 41) can be performed during the pretreatment process, specifically, between the ashing treatment (step S21) and the chemical solution treatment (step S11). Alternatively, or as shown in FIG. 11( a ), FIG. 11( b ) and FIG. 11( c ), the exposure process of the organic film pattern (step S41 ) can be performed immediately after the pre-processing starts.

In step S41, when the original organic film pattern is formed by photolithography, the organic film pattern is exposed twice, and when the original organic film pattern is formed by printing, the organic film pattern is exposed once.

In the exposure process of the organic film pattern (step 41), the organic film pattern covering at least a part of the substrate is exposed. For example, an organic film pattern that completely covers the substrate or covers at least 1/10 of the total area of the substrate is exposed. Exposure processing of the organic film pattern (step S41 ) is performed in the first processing unit 17 . In the first processing unit 17 , the organic film pattern can be fully exposed at one time, or can be scanned and exposed using a spotlight in a predetermined area. For example, the organic film pattern can be exposed to ultraviolet light, fluorescent light, or natural light.

In the fourth embodiment, it is preferable to keep the substrate in a non-photosensitive state after the initial exposure to form the organic film pattern and before step S41. By maintaining the desensitized state, it is possible to make the effect of the over-development process (step S12) uniform, or to make the total exposure of the organic film pattern uniform. All process steps may be managed in order to keep the substrate in a light-free state, or the apparatus 100 or 200 may be designed to have such a functional configuration.

The exposure processing (step S14 ) of the organic film pattern can be performed as follows.

First, an exposure process of an organic film pattern is performed by using a mask having a prescribed pattern. That is, a new pattern of the organic film pattern is determined according to the area of the organic film pattern exposed in step S41. The organic film pattern is partially removed in the subsequent over-development process (step S12 ), so that the organic film pattern becomes a new pattern. After the initial exposure for forming the organic film pattern, it is necessary to keep the organic film pattern (or the substrate) in a non-photosensitive state until step S41 is performed.

Second, by exposing the entire surface of the substrate, the over-development of the organic film pattern in step S12 can be performed more efficiently. In this case, it is not necessary to manage the photosensitive state of the organic film pattern (or the substrate) after the initial exposure for forming the organic film pattern and up to step S41. Even if the organic film pattern is exposed to some extent (for example, the organic film pattern is exposed to ultraviolet light, UV light, fluorescent light, or natural light, or placed under these lights for a long time) before performing step S41, or the exposure of an unknown degree In some cases, the substrate can be uniformly exposed by implementing step S41.

Examples of the method of the fourth embodiment are described below.

(Example 1 of the fourth embodiment)

Fig. 10(a) is a flowchart of implementation steps in Example 1 of the fourth embodiment.

As shown in FIG. 10( a), compared with the method of the first embodiment shown in FIG. 6 , in the method of Example 1 of the fourth embodiment, it is additionally included after the etching step S04 and to implement chemical solution treatment Exposure process of the organic film pattern before S11 (step S41).

The apparatus 100 or 200 used in Embodiment 1 includes a first processing unit 17 , a fifth processing unit 21 , a fourth processing unit 20 and a second processing unit 18 as processing units U1 to U9 or U1 to U7 .

(Example 2 of the fourth embodiment)

Fig. 10(b) is a flowchart of implementation steps in Example 2 of the fourth embodiment.

As shown in FIG. 10(b), compared with the method of the second embodiment shown in FIG. 8, in the method of Example 2 of the fourth embodiment, after the etching step S04 and the ashing treatment S21 are additionally included The previous exposure process of the organic film pattern (step S41).

The apparatus 100 or 200 used in Embodiment 2 includes a first processing unit 17, a sixth processing unit 22, a fourth processing unit 20, and a second processing unit 18 as processing units U1 to U9 or U1 to U7.

(Example 3 of the fourth embodiment)

Fig. 10(c) is a flowchart of implementation steps in Example 3 of the fourth embodiment.

As shown in FIG. 10(c), compared with the method of the third embodiment shown in FIG. 9, in the method of Example 3 of the fourth embodiment, after the etching step S04 and the ashing treatment S21 are additionally included The previous exposure process of the organic film pattern (step S41).

The device 100 or 200 used in Embodiment 3 includes a first processing unit 17, a sixth processing unit 22, a fifth processing unit 21, a fourth processing unit 20, and a second processing unit as processing units U1 to U9 or U1 to U7. processing unit 18.

(Example 4 of the fourth embodiment)

Fig. 10(d) is a flowchart of the implementation steps of Example 4 of the fourth embodiment.

As shown in FIG. 10( d), compared with the method of the third embodiment shown in FIG. 9 , in the method of Example 4 of the fourth embodiment, it is additionally included in the ashing treatment S21 and the implementation of chemical solution treatment Exposure processing of the organic film pattern between S11 (step S41).

The apparatus 100 or 200 used in Embodiment 4 includes a first processing unit 17, a sixth processing unit 22, a fifth processing unit 21, a fourth processing unit 20, and a second processing unit as processing units U1 to U9 or U1 to U7. processing unit 18.

(Example 5 of the fourth embodiment)

Fig. 11(a) is a flowchart of the implementation steps of Example 5 of the fourth embodiment.

As shown in FIG. 11(a), compared with the method of the first embodiment shown in FIG. 6, in the method of Example 5 of the fourth embodiment, it is additionally included in the implementation of chemical solution treatment S11 and excessive development treatment Exposure processing of the organic film pattern between S12 (step S41).

The apparatus 100 or 200 used in Embodiment 5 includes a first processing unit 17, a fifth processing unit 21, a fourth processing unit 20, and a second processing unit 18 as processing units U1 to U9 or U1 to U7.

(Example 6 of the fourth embodiment)

Fig. 11(b) is a flowchart of the implementation steps of Example 6 of the fourth embodiment.

As shown in FIG. 11(b), compared with the method of the second embodiment shown in FIG. 8, in the method of Example 6 of the fourth embodiment, the ashing process S21 and the excessive development process S12 are additionally included. The exposure process of the organic film pattern in between (step S41).

The apparatus 100 or 200 used in Embodiment 6 includes a first processing unit 17, a sixth processing unit 22, a fourth processing unit 20, and a second processing unit 18 as processing units U1 to U9 or U1 to U7.

(Example 7 of the fourth embodiment)

Fig. 11(c) is a flowchart of the implementation steps of Example 7 of the fourth embodiment.

As shown in FIG. 11(c), compared with the method of the third embodiment shown in FIG. 9, in the method of Example 7 of the fourth embodiment, it is additionally included in the implementation of the chemical solution treatment S11 and the excessive development. Exposure processing of the organic film pattern between S12 (step S41).

The device 100 or 200 used in Embodiment 7 includes a first processing unit 17, a sixth processing unit 22, a fifth processing unit 21, a fourth processing unit 20, and a second processing unit as processing units U1 to U9 or U1 to U7. processing unit 18.

Example 1 of the fourth embodiment will be described more specifically below with reference to FIG. 12 .

Figure 12(a-2), Figure 12(b-2), Figure 12(c-2) and Figure 12(d-2) are plan views respectively, and Figure 12(a-1) is Figure 12(a-2) Figure 12(b-1) is a cross-sectional view of Figure 12(b-2), Figure 12(c-1) is a cross-sectional view of Figure 12(c-2), Figure 12(d-1) is The sectional view of Fig. 12(d-2).

As shown in FIG. 12( a-1 ) and FIG. 12( a-2 ), a gate electrode 602 having a predetermined shape is formed on an insulating substrate 601 . A gate insulating film 603 is formed on the insulating substrate 601 to cover the gate electrode 602, and then an amorphous silicon layer 604, an N+ amorphous silicon layer 605 and a source/drain layer are sequentially stacked on the gate insulating film 603 606.

As shown in FIG. 12( b-1 ) and FIG. 12( b-2 ), an organic film pattern 607 is formed on the source/drain layer 606 . Then, the source/drain layer 606 , the N+ amorphous silicon layer 605 and the amorphous silicon layer 604 are etched using the organic film pattern 607 as a mask. In this way, the gate insulating film 603 appears only in the region where the organic film pattern 607 is not formed.

The initial organic film pattern 607 is different from the initial organic film pattern shown in FIG. 7(b-1) in that it has a uniform thickness.

Then, pre-processing, main processing, and exposure processing S41 of the organic film pattern are performed in the order described in performing any one of Examples 1-7 (FIGS. 10 and 11) of the present embodiment above.

The exposure process S41 of the organic film pattern is performed by using a mask having a predetermined pattern. In the subsequent over-development process (step S12 ), the organic film pattern 607 is processed into a new pattern, as shown in FIG. 7(c-1) and FIG. 7(c-2). That is, the original organic film pattern 607 is divided into a plurality of parts (two parts in FIG. 12 ).

Then, the source/drain layer 606 and the N+ amorphous silicon layer 605 are etched using the organic film pattern 607 as a mask to reveal the amorphous silicon layer 604 and the organic film pattern 607 is removed.

When the bottom film under the organic film pattern is composed of multiple layers, the bottom film is etched using the organic film pattern as a mask before and after the pretreatment, main treatment, and organic film pattern exposure treatment, so that the overdeveloped The region etched in the etching process (step S04 ) performed before the process (step S12 ) and the region etched in the etching process performed after steps S12 and S13 are different from each other. Therefore, the first layer (such as the amorphous silicon layer 604) and the second layer (such as the source/drain layer 606 and the N+ amorphous silicon layer 605) of the multiple layers of the bottom film can be etched to form mutual different patterns.

Example 2 of the fourth embodiment will be described more specifically below with reference to FIG. 13 .

Figure 13(a-2), Figure 13(b-2), Figure 13(c-2) and Figure 13(d-2) are plan views respectively, and Figure 13(a-1) is Figure 13(a-2) Figure 13(b-1) is a cross-sectional view of Figure 13(b-2), Figure 13(c-1) is a cross-sectional view of Figure 13(c-2), Figure 13(d-1) is The sectional view of Fig. 13(d-2). The organic film pattern is omitted in FIG. 13(b-2) and FIG. 13(c-2).

As shown in FIG. 13( a-1 ) and FIG. 13( a-2 ), a gate electrode 602 having a predetermined shape is formed on an insulating substrate 601 . A gate insulating film 603 is formed on the insulating substrate 601 so as to cover the gate electrode 602 . A source/drain electrode 801 of a predetermined shape is formed on the gate insulating film 603 , and a cover film 802 made of an insulating material is formed on the gate insulating film 603 so as to cover the source/drain electrode 801 .

As shown in FIGS. 13( b-1 ) and 13 ( b-2 ), an initial organic film pattern 607 is formed on the cover film 802 . Then, the cover film 802 and the gate insulating film 603 are etched using the organic film pattern 607 as a mask. In this way, the gate electrode 602 appears in the area not covered by the original organic film pattern 607 .

The initial organic film pattern 607 is different from the initial organic film pattern shown in FIG. 7(b-1) in that it has a uniform thickness.

Then, pre-processing, main processing, and exposure processing S41 of the organic film pattern are performed in the order described in any one of the above-mentioned Embodiments 1-7 (FIGS. 10 and 11).

Exposure processing S41 of the organic film pattern 607 is performed using a mask having a predetermined pattern. Therefore, the organic film pattern 607 is processed into a new pattern in the subsequent over-development process (step S12 ) as shown in FIG. 13( c-1 ).

Then, as shown in FIGS. 13(c-1) and 13(c-2), the cover film 802 is etched using the organic film pattern 607 obtained in the main process as a mask, and as a result, the source/drain electrodes 801 are partially is developed, and then the organic film pattern 607 is removed.

When the bottom film under the organic film pattern is composed of multiple layers, the bottom film is etched using the organic film pattern as a mask before and after the pretreatment, main treatment, and organic film pattern exposure treatment, so that the overdeveloped The region etched in the etching process (step S04 ) performed before the process (step S12 ) and the region etched in the etching process performed after steps S12 and S13 are different from each other. Therefore, the first layer (for example, the gate insulating layer 603 ) and the second layer (for example, the cover film 802 ) among the plurality of layers of the base film may be etched to form different patterns from each other.

After etching the gate insulating film 603 and the cover film 802 on the gate electrode 602, only the cover film 802 on the source/drain electrode 801 is etched to prevent the source/drain electrode 801 from being damaged.

Since the method of the fourth embodiment additionally includes the exposure treatment (step 41) of the organic film pattern compared with the methods of the first to third embodiments, even if the initial organic film pattern has a uniform thickness (ie , when the initial organic film pattern does not have at least two portions with different thicknesses), the organic film may be subjected to patterning treatment to form a new pattern.

Alternatively, the method of the fourth embodiment, which additionally includes exposure processing (step 41 ) of the organic film pattern, can effectively perform overdevelopment processing (step S12 ) even when the organic film pattern is not processed into a new pattern.

The selection policy of the preprocessing in each of the above-mentioned embodiments will be described below.

FIG. 14 shows the degree of deterioration of the degenerated layer according to the cause of the degenerated layer. In FIG. 14 , the degree of deterioration was determined based on the difficulty of wet stripping the deteriorated layer.

As shown in Figure 14, the degree of degeneration of the degenerated layer mainly depends on the chemical solution used in the wet etching, whether the dry etching process is isotropic or anisotropic, whether there are deposits on the organic film pattern, and whether the wet etching process is isotropic or anisotropic. The gas used in the etching process. Therefore, the ease of removal of the degenerated layer also depends on those factors.

The chemical solution used in the chemical solution treatment (step S11 ) on the organic film pattern can be selected from acid solution, alkali solution or organic solvent, or a combination thereof.

Specifically, the medicinal solution is selected from alkaline aqueous solutions or aqueous solutions containing at least one amine material as an organic solvent, wherein the content of the amine material is 0.05 to 10% by weight.

Wherein, the amine material is selected from monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, Tributylamine, hydroxylamine, diethylhydroxylamine, dehydrated diethylhydroxylamine, pyridine, or picoline.

If the degree of deterioration of the degenerated layer is relatively small, that is, if the degenerated layer is formed due to oxidation caused by aging, acid etchant, isotropic oxygen ashing treatment, the content of the amine material in the selected liquid is 0.05 to 3 wt. %.

15 is a schematic diagram of the relationship between the concentration of amine materials in the chemical solution and the removal efficiency of organic film patterns.

As shown in FIG. 15, it is preferable that the chemical solution contains 0.05 to 1.5% by weight of an amine material as an organic solvent to remove only the degenerated layer of the organic film pattern while leaving the undegenerated part. For this reason, it is preferred that the drug solution contains an amine material selected from hydroxylamine, diethylhydroxylamine, dehydrated diethylhydroxylamine, pyridine or picoline. For preservatives, D-glucose (C ₆ H ₁₂ O ₆ ), chelating agents or antioxidants can be chosen.

By setting the implementation time of the chemical solution treatment (step S11) on the organic film pattern, and selecting an appropriate chemical solution, only the deteriorated layer or deposited layer on the organic film pattern can be removed, and the part without deterioration or the deposited layer can be kept. A filmy pattern of layer coverage emerges.

The advantage of applying the chemical solution treatment (step S11) to the organic film pattern is that the chemical solution having the function of developing the organic film pattern can easily penetrate into the organic film pattern in the over-development process (step S12) performed after step S11. middle.

Actually, by applying the chemical solution to the surface of the organic film pattern, the degenerated layer can be cracked, or part or all of the degenerated layer can be removed. Therefore, it is possible to prevent the deteriorated layer from obstructing the chemical solution having the function of developing the organic film pattern from penetrating into the organic film pattern during the over-development process.

It is important that the non-deteriorated part of the organic film pattern cannot be removed but should remain, and the chemical solution can easily penetrate into the non-deteriorated part of the organic film pattern by removing only the degenerated layer or cracking the degenerated layer. It is necessary to select a medicinal solution that can exert the said effect.

When the formed metamorphic layer or deposition layer is very firm, or thicker, or quite difficult to remove, it is preferable to remove it as shown in Fig. 8, Fig. 9, Fig. 10(b), Fig. 10(c), Fig. The ashing treatment shown in (b) and FIG. 11(c) is performed alone or in combination with chemical solution treatment on the organic film pattern. By performing such ashing treatment alone or in combination with chemical solution treatment, it is possible to solve the problems that the degenerated layer is difficult to remove or takes too much time to remove by chemical solution treatment alone.

Fig. 16 shows the change of the degenerated layer when only oxygen (O ₂ ) ashing treatment or isotropic plasma treatment is performed on the degenerated layer, and Fig. 17 shows that only the chemical solution treatment (using an aqueous solution containing 2% hydroxylamine) is performed on the degenerated layer. ) changes in the altered layer, and FIG. 18 shows changes in the altered layer when the above-mentioned ashing treatment and the above-mentioned chemical solution treatment are sequentially performed on the altered layer. In FIGS. 16 to 18 , similarly to FIG. 14 , the degree of deterioration is determined according to the difficulty procedure of wet stripping the deteriorated layer.

In either case, as shown in Figs. 16 to 18, the degenerated layer can be removed. However, when comparing the oxygen ashing treatment (isotropic plasma treatment) shown in FIG. Depending on the characteristics, the degree of removal of the metamorphic layer is also different.

As shown in FIG. 16, the oxygen ashing treatment (isotropic plasma treatment) is relatively effective in removing the degenerated layer with deposits, but tends to cause damage to the object. Therefore, if oxygen ashing treatment (isotropic plasma treatment) is performed on the degenerated layer without deposits thereon, the degenerated layer remains to a greater extent than when only chemical solution treatment is performed on the degenerated layer ( FIG. 15 ).

In contrast, as shown in FIG. 17 , applying a chemical solution (aqueous solution containing 2% hydroxylamine) to the degenerated layer is not as effective as oxygen ashing in removing the degenerated layer with deposits, but does not cause damage. Therefore, if the chemical liquid treatment is performed on the degenerated layer without deposits thereon, the extent of the remaining degenerated layer treated only with oxygen ashing treatment is greater.

Therefore, in order to have the advantages shown in FIGS. 16 and 17, as shown in FIG. 18, oxygen ashing treatment (isotropic plasma treatment) and chemical solution (using an aqueous solution containing 2% hydroxylamine were used) were sequentially performed on the degenerated layer. )deal with. It will be appreciated that the method shown in FIG. 18 works both with and without deposits of the degenerated layer, while removing the degenerated layer under conditions where damage can be suppressed.

In each of the above-mentioned embodiments, the main processing includes over-processing of organic film development (step S12 ) and heating of the organic film pattern (step S13 ). The main treatment may include performing chemical solution treatment on the organic film pattern, wherein the chemical solution does not have the function of developing the organic film pattern but has the function of dissolving the organic film pattern. For example, such a drug solution can be obtained by diluting a separating agent. Specifically, the medicinal solution can be obtained by diluting the concentration of the separating agent to a concentration of 20% or less. Preferably the concentration of separating agent is at least 2%. For example, the drug solution can be obtained by diluting the separating agent with water.

In the above-described embodiments, the organic film pattern is mainly composed of the organic photosensitive film. When the organic film pattern is formed by a printing method, and when the main treatment is performed using a chemical solution that does not have the function of developing the organic film pattern but has the function of dissolving the organic film pattern, the organic film pattern does not always need to be composed of a photosensitive organic film. In addition, in this case, the exposure process S41 of the organic film pattern may not be necessary.

Even if the organic film pattern is formed by a printing method, it may be composed of an organic photosensitive film, and the exposure process S41 of the organic film pattern may be performed.

The method of the above embodiment may further include the step of heating the organic film pattern. The purpose of performing the step of heating the organic film pattern is to remove moisture, acid solution and/or alkali solution infiltrated into the organic film pattern, or restore the adhesive force between the organic film pattern and the base film when the adhesive force decreases. For example, the organic film pattern is heated at a temperature of 50 to 150° C. for 60 to 300 seconds.

The organic film pattern can be completely removed in the method of the above-described embodiments. This means that the methods of the above-described embodiments or parts thereof can be used to peel or separate organic film patterns. Specifically, as a first example, by using a chemical solution that can remove not only the degenerated layer and/or the deposited layer but also the organic film pattern, and the implementation time of the pretreatment in the embodiment (that is, where the The pretreatment time without completely removing the organic film pattern) The pretreatment can be carried out for a longer period of time to completely remove the organic film pattern. As a second example, the altered layer or the deposited layer is removed in the pre-treatment, and the time is longer than that of the main treatment in the embodiment (i.e., the time in which the main treatment is performed without completely removing the organic film pattern) The internal main treatment can completely remove the organic film pattern.

Claims (60)

1. the processing method of the organic film pattern that forms on the substrate, it comprises: The first step is removing the altered layer or deposited layer by applying a chemical solution to the altered layer or deposited layer formed on the surface of the organic film pattern; and In the second step, at least a part of the organic film pattern is reduced, or a part of the organic film pattern is deformed. 2. the processing method of the organic film pattern that forms on the substrate described in claim 1, it comprises: The first step is to remove the degenerated layer formed on the surface of the organic film pattern by applying a chemical solution to the degenerated layer or deposition layer formed on the surface of the organic film pattern, so that the unmodified part of the organic film pattern is revealed; and In the second step, at least a part of the organic film pattern is reduced, or a part of the organic film pattern is deformed. 3. The method of claim 1 or 2, wherein the deteriorated layer is caused by at least one of deterioration of the surface of the organic film pattern due to aging, thermal oxidation, and thermal hardening. 4. The method of claim 1 or 2, wherein the altered layer is caused by wet etching the organic film pattern using a wet etchant. 5. The method of claim 1 or 2, wherein the altered layer is caused by dry etching or ashing of the organic film pattern. 6. The method of claim 1 or 2, wherein the altered layer is caused by deposits caused by dry etching of the organic film pattern. 7. the processing method of the organic film pattern that forms on the substrate as claimed in claim 1, it comprises: The first step is to remove the deposited layer formed on the surface of the organic film pattern by applying a chemical solution to the degenerated layer or deposited layer formed on the surface of the organic film pattern, so that the organic film pattern appears; and In the second step, at least a part of the organic film pattern is reduced, or a part of the organic film pattern is deformed. 8. The method according to claim 1 or 7, wherein the deposited layer is formed on the surface of the organic film pattern by dry etching the organic film pattern. 9. The method of claim 1, 2 or 7, wherein the organic film pattern is formed by a printing method. 10. The method of claim 1, 2 or 7, wherein the organic film pattern is formed by photolithography. 11. The method according to claim 1, 2 or 7, wherein the second step includes a step of developing the organic film pattern using a chemical solution having a function of developing the organic film pattern. 12. The method according to claim 11, wherein the chemical solution is composed of an alkaline aqueous solution containing tetramethylammonium hydroxide, or an inorganic alkaline aqueous solution. 13. The method of claim 12, wherein the aqueous inorganic base solution is selected from NaOH and Ca(OH) ₂ . 14. The method according to claim 1, 2 or 7, wherein the second step is to perform a Kth development process on the organic film pattern, wherein K is an integer equal to or greater than 2. 15. The method according to claim 1, 2 or 7, wherein the second step consists of a step of applying a chemical liquid to the organic film pattern, the chemical liquid does not have the function of developing the organic film pattern, But it has the function of dissolving the organic film pattern. 16. The method of claim 15, wherein the medicinal solution is obtained by diluting a separating agent. 17. The method of claim 1, 2 or 7, wherein the second step consists of a step of separating at least one organic film pattern into a plurality of parts. 18. The method according to claim 1 , 2 or 7, further comprising a third step of patterning the base film under the organic film pattern using the organic film pattern that has not been processed as a mask deal with. 19. The method according to claim 1, 2 or 7, wherein the second step is to deform the organic film pattern so that the organic film pattern becomes a pattern covering the circuit pattern formed on the substrate. Insulation film is constructed in steps. 20. The method according to claim 1 , 2 or 7, further comprising a fourth step of using the processed organic film pattern as a mask to perform patterning treatment on the base film under the organic film pattern . 21. The method of claim 18, wherein the base film is patterned into a tapered or stepped shape. 22. The method of claim 20, wherein the base film is patterned into a tapered or stepped shape. 23. The method of claim 18, wherein the base film is composed of a plurality of films, at least one of which is subjected to a pattern forming process to have a pattern different from the other patterns. 24. The method of claim 20, wherein the base film is composed of a plurality of films, at least one of which is patterned into a pattern different from other patterns. 25. The method of claim 1, 2 or 7, wherein at least part of the first step is performed by subjecting the organic film pattern to an ashing process. 26. The method of claim 1, 2, or 7, wherein at least a portion of the first step is performed by applying a chemical solution to the organic film pattern. 27. The method of claim 1, 2 or 7, wherein at least a part of the first step is performed by applying a chemical solution and performing ashing treatment to the organic film pattern. 28. The method according to claim 27, wherein the ashing process is performed on the organic film pattern and the chemical solution is applied to the organic film pattern in sequence. 29. The method of claim 26, wherein the first step is performed entirely by applying a chemical solution to the organic film pattern. 30. The method according to claim 1, 2 or 7, wherein the first step is completely performed by sequentially performing ashing treatment on the organic film pattern and applying a chemical solution to the organic film pattern. 31. The method of claim 26, wherein the medical solution contains at least an acidic chemical. 32. The method according to claim 26, wherein the medical solution contains at least an organic solvent. 33. The method of claim 26, wherein the medical solution contains at least an alkaline chemical. 34. The method of claim 32, wherein the organic solvent contains at least an amine-based material. 35. The method of claim 26, wherein the chemical solution contains at least an organic solvent and an amine-based material. 36. The method of claim 33, wherein the alkaline chemical comprises at least an amine material and water. 37. The method of claim 26, wherein the medical solution contains at least an alkaline chemical and an amine material. 38. The method of claim 34, wherein the amine material is selected from the group consisting of: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine Amine, monobutylamine, dibutylamine, tributylamine, hydroxylamine, diethylhydroxylamine, dehydrated diethylhydroxylamine, pyridine, and picoline. 39. The method of claim 34, wherein the content of the amine material in the liquid medicine ranges from 0.01% to 10% by weight, inclusive. 40. The method of claim 34, wherein the content of the amine material in the liquid medicine ranges from 0.05% to 3% by weight, inclusive. 41. The method of claim 34, wherein the content of the amine-based material in the liquid medicine ranges from 0.05% to 1.5% by weight, inclusive. 42. The method of claim 26, wherein the medical fluid comprises a preservative. 43. The method of claim 1, 2 or 7, further comprising a fifth step of exposing the organic film pattern, the fifth step being performed prior to the first step. 44. The method of claim 1 , 2 or 7, further comprising a fifth step of exposing the organic film pattern, the fifth step being performed during the first step. 45. The method of claim 1, 2 or 7, further comprising a fifth step of exposing the organic film pattern, the fifth step being performed between the first and second steps. 46. The method of claim 43, wherein the organic film pattern is exposed only in an area related to a predetermined area of the substrate. 47. The method of claim 46, wherein the organic film pattern is exposed within the area by irradiating light to the entire area or by scanning the area using a spotlight. 48. The method of claim 46, wherein the area of the predetermined region is at least 1/10 of the area of the substrate. 49. The method of claim 46, wherein a new pattern of the organic film pattern is determined according to an implementation area of the fifth step. 50. The method of claim 49, wherein an area where the fifth step is performed is determined to separate at least a part of the organic film pattern into a plurality of parts. 51. The method of claim 46, wherein the organic film pattern is exposed to ultraviolet light, fluorescent light, or natural light. 52. The method of claim 25, wherein the ashing step consists of a step of etching a film formed on the substrate using at least one of plasma, ozone, and ultraviolet rays. 53. The method of claim 1, 2 or 7, wherein the organic film pattern initially formed on the substrate has at least two portions having different thicknesses from each other. 54. The method of claim 1, 2 or 7, wherein the organic film pattern initially formed on the substrate has at least two portions having different thicknesses from each other, and the second step makes the portion having a small thickness further thinned. 55. The method of claim 1 , 2 or 7, wherein the organic film pattern initially formed on the substrate has at least two portions having different thicknesses from each other, and the second step converts the portion having a small thickness to remove. 56. The method of claim 1, 2 or 7, wherein the organic film pattern remains in a non-photosensitive state before performing the first step. 57. A medicinal liquid for use in the method of claim 34, wherein the content of the amine-based material in the medicinal liquid ranges from 0.01% by weight to 10% by weight, inclusive. 58. The medical solution of claim 57, wherein the content of the amine-based material in the medical solution ranges from 0.05% by weight to 3% by weight, inclusive. 59. The medicinal liquid of claim 58, wherein the content of the amine-based material in the medicinal liquid ranges from 0.05% by weight to 1.5% by weight, inclusive. 60. The medical solution of claim 57, wherein the amine-based material is selected from the group consisting of hydroxylamine, diethylhydroxylamine, dehydrated diethylhydroxylamine, pyridine, and picoline.

Images